Effect of Molecular Symmetry on the Spectra and Dynamics of the Intramolecular Charge Transfer (ICT) state of peridinin.

The spectroscopic properties and dynamics of the excited states of two different synthetic analogues of peridinin were investigated as a function of solvent polarity using steady-state absorption, fluorescence, and ultrafast time-resolved optical spectroscopy. The analogues are denoted S-1- and S-2-peridinin and differ from naturally occurring peridinin in the location of the lactone ring and its associated carbonyl group, known to be obligatory for the observation of a solvent dependence of the lifetime of the S(1) state of carotenoids. Relative to peridinin, S-1- and S-2-peridinin have their lactone rings two and four carbons more toward the center of the π-electron system of conjugated carbon-carbon double bonds, respectively. The present experimental results show that as the polarity of the solvent increases, the steady-state spectra of the molecules broaden, and the lowest excited state lifetime of S-1-peridinin changes from ∼155 to ∼17 ps which is similar to the magnitude of the effect reported for peridinin. The solvent-induced change in the lowest excited state lifetime of S-2-peridinin is much smaller and changes only from ∼90 to ∼67 ps as the solvent polarity is increased. These results are interpreted in terms of an intramolecular charge transfer (ICT) state that is formed readily in peridinin and S-1-peridinin, but not in S-2-peridinin. Quantum mechanical computations reveal the critical factors required for the formation of the ICT state and the associated solvent-modulated effects on the spectra and dynamics of these molecules and other carbonyl-containing carotenoids and polyenes. The factors are the magnitude and orientation of the ground- and excited-state dipole moments which must be suitable to generate sufficient mixing of the lowest two excited singlet states.